EP0405222A2 - Procédé de préparation d'alpha-oléfines - Google Patents

Procédé de préparation d'alpha-oléfines Download PDF

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Publication number
EP0405222A2
EP0405222A2 EP90111098A EP90111098A EP0405222A2 EP 0405222 A2 EP0405222 A2 EP 0405222A2 EP 90111098 A EP90111098 A EP 90111098A EP 90111098 A EP90111098 A EP 90111098A EP 0405222 A2 EP0405222 A2 EP 0405222A2
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EP
European Patent Office
Prior art keywords
ethylene
displacement
chain growth
olefins
product
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Application number
EP90111098A
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German (de)
English (en)
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EP0405222B1 (fr
EP0405222A3 (en
Inventor
Alvin Earl Harkins
Layne Woods Summers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos USA LLC
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Ethyl Corp
Albemarle Corp
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Publication of EP0405222A2 publication Critical patent/EP0405222A2/fr
Publication of EP0405222A3 publication Critical patent/EP0405222A3/en
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Publication of EP0405222B1 publication Critical patent/EP0405222B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/88—Growth and elimination reactions

Definitions

  • Alpha-olefins are made in commercial quantities by a process initially developed in the fifties by Karl Ziegler and his co-workers.
  • the so-called Ziegler process involves the reaction of triethyl aluminum (“TEA”) and ethylene at temperatures in the range of 200-500 F and pressure in the range of 2000-5000 psig to yield a mixture of tri-C 2 - 20 + alkyl aluminum having a poisson alkyl distribution and C 2 - 20 olefins.
  • the ethylene is flashed from the reaction mixture for recycle and the light olefins through decene-1 can be distilled from the mixed aluminum alkyls since they have a normal boiling point below the lightest aluminum alkyl (viz. TEA).
  • Johnson, U.S. 2,863,896 describes the preparation of pure aluminum alkyls using a chain growth reaction of a C2-4- olefin (e.g. ethylene) with a low molecular weight trialkyl aluminum (e.g. TEA), dialkyl aluminum hydride or alkyl aluminum dihydride.
  • the chain growth product contained 2-5 percent C 4-20 olefin which could not be separated from the aluminum alkyls.
  • the mixture was then subjected to a displacement reaction with a C 4 - 6 ⁇ -olefin, e.g. 1-butene, to displace mainly C 6-20 a-olefin forming tributyl aluminum.
  • the C 6 - 20 a-olefins were fractionated into individual a-olefins. These individual a-olefin cuts were then reacted in a second displacement reaction with the tributyl aluminum formed in the butene displacement reaction to form pure trialkyl aluminum.
  • All aluminum alkyl chain growth products initially yield a mixture of higher trialkyl aluminum compounds exhibiting a poisson distribution.
  • the mixture is mainly tri-C 2-20 alkyl aluminum compounds although a small amount of C 2 ⁇ + alkyls are usually present.
  • Ethylene displacement of this mixture yields a mixture of C 2 - 20 olefins.
  • the more valuable components are the C s - 14 a-olefins.
  • Ethylene can be recycled to chain growth and olefins above C 14 can be separated for use as diluent or can be purged.
  • Butene is produced in fairly large amounts and cannot economically be discarded.
  • the commercial market for butene is substantially saturated.
  • the present invention provides a process that utilizes the butene that it produces in a closed butene displacement loop that gives high yield of the more desirable C 6-12 a-olefins.
  • C 6-14 a-olefins are produced in high yield without the need to dispose of butene by-product by conducting an initial TEA/ethylene chain growth step, distilling ethylene and C 4 - 14 olefins from this chain growth product and conducting at least one ethylene displacement step on the resultant distillation bottoms.
  • This displacement forms TEA and C 4 - 20 a-olefin.
  • the ethylene is separated for recycle and the C 4-12 olefins and part of the C 14 olefins are separated from the remaining C, 4 + olefins and TEA.
  • the C 4-14 a-olefins are distilled to separate 1-butene and various C 6-14 olefin fractions.
  • the 1-butene produced in the ethylene/TEA chain growth-ethylene displacement loop is utilized in a butene displacement loop in which ethylene/TEA chain growth product is distilled to remove ethylene and C 4 - 12 a-olefins and part of the C 14 olefins and a portion of the bottoms are subjected to butene displacement.
  • Lower olefins can be distilled from the butene displacement product if desired and the butene displacement product is then subjected to ethylene chain growth to form a mixture of C 2 - 20 olefins and tri-C 2 - 20 alkyl aluminums.
  • Ethylene is vaporized from this and the remainder is recycled to the olefin distillation zone following the initial TEA/ethylene chain growth.
  • the drawing is a schematic flow diagram of the process. Conventional equipment such as valves, pumps, heaters, coolers and the like have not been included in the drawing for the sake of improved clarity.
  • C2 is ethylene and C4 is butene.
  • a poisson distribution of trialkyl aluminum is designated by “p” followed by “tri-C n alkyl aluminum” where the subscript "n” represents the number of carbon atoms in the alkyl groups or a range of carbon atoms in the alkyl groups.
  • p tri-C 2 - 2 o alkyl aluminum represents a mixture of trialkyl aluminums in which the alkyl groups contain from 2 to 20 carbon atoms. The moles of each particular alkyl group in the mixture varies in a poisson distribution.
  • a preferred embodiment of the invention is a process for making C 6-14 a-olefins said process including a butene displacement loop, said process comprising:
  • a still further preferred embodiment of the invention includes both a C 4 - 8 olefin displacement loop and an ethylene displacement loop.
  • any C 4 - 8 olefin formed in either loop can be used as feed.
  • This dual loop process includes steps (A) through (G) as stated above and also includes the additional steps of:
  • a most preferred embodiment of the dual loop process includes steps (A) through (G) as set forth above and also the additional steps of:
  • the process is best described by reference to the drawing.
  • the drawing is a schematic flow diagram of a preferred embodiment of the process including ethylene chain growth, a 2-stage ethylene displacement loop and a butene displacement-ethylene displacement loop.
  • TEA triethyl aluminum
  • Chain growth reactor 1 is maintained under chain growth conditions. These are a temperature in the range of 200-500 F, more preferably 225-350 F, and a pressure of 2000-5000 psig, more preferably 2000-3500 psig.
  • Residence time of ethylene and TEA in chain growth reactor 1 should be long enough to increase the chain length of the alkyls bonded to aluminum to a mole average chain length of 6-12 carbon atoms. Depending on temperature and pressure, a residence time on the order of 15 minutes to 1 hour is usually satisfactory.
  • the first chain growth product formed in chain growth reactor 1 is conveyed via conduit 2 into vapor-liquid separator 3 which is at a lower pressure than chain growth reactor 1 causing most of the residual ethylene in the first chain growth product to vaporize and be removed overhead. All ethylene streams separated in the process are recycled to one of the ethylene chain growth reactors or ethylene displacement reactors which consume all the separated ethylene.
  • distillation unit 6 which serves to distill out C 4-10 olefins.
  • Distillation unit 6 is shown as a single unit but is preferably a series of 2-3 separation units each in sequence at a lower pressure than the preceding unit.
  • distillation unit 6 The bottoms from distillation unit 6 are transferred via conduit 7 to a mid-point in vacuum rectification column 8 .
  • Column 8 is operated in a range of 5-30 torr with its reboiler adjusted to maintain reflux conditions in the rectification zone above the mid-point in a temperature range of 200-250 F. Under these conditions, 1-dodecene together with some 1-decene and 1-tetradecene are distilled overhead with little contamination by TEA which has about the same normal boiling point.
  • the C 4 - 14 olefins removed are transferred to a distillation area (not shown) where they are combined with olefins recovered from other sections of the overall process and fractionated to recover butene for feed to the butene displacement unit to be described later and to form olefin fractions, e.g. 1-octene, 1-decene, 1-dodecene, suitable for sales.
  • olefin fractions e.g. 1-octene, 1-decene, 1-dodecene, suitable for sales.
  • other C 4 - 8 a-olefins can be combined and used as feed to the butene displacement reactor in which case it should be referred to as a C 4-8 olefin displacement reactor.
  • the olefin in excess over demand in the overall process is 1-butene.
  • Linear low density polyethylene provide a market for all 1- hexene. Excess 1-octene can be combined with the 1-butene as feed to the C 4-8 olefin displacement reactor. However, in a most preferred embodiment the C 4 - 8 olefin is mainly, i.e. 60-100 weight percent and preferably 75-100 weight percent and most preferably 90-100 weight percent, 1-butene.
  • the bottoms stream from vacuum column 8 comprises mainly poisson distributed tri-C 2 - 20 + alkyl aluminums and C 14 + olefins. A portion of this stream depending on the amount of 1-butene available but generally 75-95 weight percent is conveyed via conduits 10 and 11 to butene displacement zone 12 .
  • Butene displacement zone 12 is maintained under displacement conditions. This requires a temperature in the range of 500-750 °F and a pressure of 1000-2000 psig.
  • 1-butene is pumped into zone 12 in an amount sufficient to provide 3.5-10 moles of 1-butene per mole of aluminum alkyl.
  • the displacement reaction is fast. An average residence time of 0.1 to 1 second is usually adequate. This results in butene displacement of most of the alkyl groups bonded to aluminum forming a butene-displaced product comprising mainly tributyl aluminum, residual tri-C 2 - 20 alkyl aluminum, ethylene and C 4 - 20 + a-olefins.
  • the butene-displaced product is transferred via conduit 15 to distillation unit 16 which functions to flash off ethylene and distill out C 4-10 a-olefins.
  • the ethylene is recycled to chain growth and the C 4-10 olefins are transferred to the distillation area mentioned earlier for separation into various fractions.
  • the bottoms stream from distillation unit 16 is transferred via conduit 17 to second ethylene chain growth reactor 20 maintained under chain growth conditions. These conditions are the same as in the first ethylene chain growth reaction zone, i.e. 200-500 F, 2000-5000 psig, residence time 15 minutes to 1 hour.
  • Ethylene is fed to second ethylene chain growth reactor 20 in an amount sufficient to increase the average chain length of the alkyls to 6-8 carbon atoms. This usually requires 3-6 moles of ethylene per mole of aluminum alkyl. This results in a second chain growth product comprising mainly ethylene, C 4 - 20 a-olefins and tri-C 4-20 alkyl aluminum.
  • the second chain growth product is conveyed via conduit 21 to ethylene separator 22 wherein ethylene is flashed off at a lower pressure.
  • the ethylene-depleted liquid phase from separator 22 comprises mainly C 4 - 20 a-olefins and tri-C 2-20 alkyl aluminums and is conveyed via conduit 23 back to conduit 5 leading to distillation unit 6, thus completing the butene loop.
  • second chain growth product from reactor 20 is transferred from conduit 21 via conduit 24 (shown as dashed line) to vapor-liquid separator 3wherein ethylene separation is performed.
  • ethylene displacement zone 31 maintained under ethylene displacement conditions. These are 450-700 F at 200-400 psig with an average residence time of 0.1-5 seconds. Ethylene is also pumped into displacement zone 31 in an amount sufficient to displace most of the non-ethyl alkyl groups bonded to aluminum. This requires 5-10 moles of ethylene per mole of aluminum alkyl.
  • this stream is subject to a flash vaporization to remove most of the ethylene and the liquid phase is further distilled to remove C 4 - 12 a-olefins and the distillation bottoms are recycled to the first ethylene chain growth reaction zone.
  • the more preferred ethylene displacement loop uses two ethylene displacement operations.
  • ethylene displacement zone 31 is referred to as first ethylene displacement zone 31 .
  • the amount of ethylene pumped to displacement zone 31 is adjusted such that under the displacement conditions used, only 75-95 mole percent of the aluminum alkyls form TEA resulting in a partially displaced product comprising mainly ethylene, tri-C 2 - 20 alkyl aluminum and C 4 - 20 a-olefins.
  • the partially displaced product is conveyed via conduit 32 to distillation unit 33 which functions to distill out C 2-12 olefins and part of the TEA forming a bottoms fluid comprising mainly tri-C 2 - 20 alkyl aluminum and C 14 - 20 olefins.
  • This bottoms fluid is conveyed via conduit 34 to second ethylene displacement unit 35 maintained under ethylene displacement conditions.
  • Ethylene is fed to second ethylene displacement unit 35 in an amount sufficient to complete the displacement of non-ethyl alkyl groups bonded to aluminums forming a second ethylene-displaced product comprising mainly ethylene, C 4-20 + a-olefins and TEA.
  • This second ethylene-displaced product is transferred via conduit 40 to distillation unit 41 which functions to distill ethylene, C 4 - 12 a-olefin and part of the remaining TEA overhead.
  • This distillate is combined via conduit 42 with the overhead stream from distillation unit 33 and the combined stream 43 is subjected to flash vaporization in flash unit 45 to remove ethylene.
  • the ethylene-depleted bottoms mixture from flash unit 45 is conveyed via conduit 46 to distillation unit 47 wherein C 4 - ⁇ a-olefins are distilled overhead and the bottoms stream comprising TEA and residual C 8-12 olefins is conveyed via conduit 48 back to first ethylene chain growth reaction zone as part of the TEA feed. This completes the ethylene displacement loop.
  • the bottoms from distillation unit 41 are conducted via conduit 50 to a mid-point in vacuum rectification column 51 maintained at 15-30 torr.
  • TEA is distilled overhead for recycle and the bottoms stream comprising mainly heavy C 14 + olefins and heavy aluminum alkyls is conveyed to a disposal area as a purge stream.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP90111098A 1989-06-29 1990-06-12 Procédé de préparation d'alpha-oléfines Expired - Lifetime EP0405222B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/373,247 US4935569A (en) 1989-06-29 1989-06-29 Alpha-olefin process
US373247 1989-06-29

Publications (3)

Publication Number Publication Date
EP0405222A2 true EP0405222A2 (fr) 1991-01-02
EP0405222A3 EP0405222A3 (en) 1992-02-26
EP0405222B1 EP0405222B1 (fr) 1995-10-18

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EP90111098A Expired - Lifetime EP0405222B1 (fr) 1989-06-29 1990-06-12 Procédé de préparation d'alpha-oléfines

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US (1) US4935569A (fr)
EP (1) EP0405222B1 (fr)
JP (1) JP2744118B2 (fr)
CA (1) CA2018327C (fr)
DE (1) DE69023050T2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157190A (en) * 1990-04-02 1992-10-20 Ethyl Corporation Process for preparing olefins by butene displacement
US5233103A (en) * 1992-06-29 1993-08-03 Ethyl Corporation Preparation of organoaluminum compounds and linear alcohols derived therefrom
US5518932A (en) * 1993-06-21 1996-05-21 Albemarle Corporation Control of ethylene on alkyl aluminum chain growth processes using calorimetry
US5498735A (en) * 1993-08-05 1996-03-12 Idemitsu Petrochemical Co., Ltd. Process of producing α-olefin
CN1048977C (zh) * 1995-11-15 2000-02-02 中国石油化工总公司 制备低碳α－烯烃的方法
JPH11266049A (ja) * 1998-03-17 1999-09-28 Fujitsu Ltd 発光素子駆動装置
US6111156A (en) * 1998-11-10 2000-08-29 Nova Chemicals (International) S.A. Integrated high temperature high conversion olefin/polyolefin process
DE10238027A1 (de) * 2002-08-20 2004-03-04 Basf Ag Kombiniertes Verfahren zur selektiven Herstellung von alpha-Olefinen
WO2007011462A1 (fr) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Lubrifiants obtenus à partir de charges d'alpha-oléfines mélangées
JP5575267B2 (ja) 2009-12-24 2014-08-20 エクソンモービル・ケミカル・パテンツ・インク 新規合成ベースストックの製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1173508A (fr) * 1956-04-10 1959-02-26 Exxon Research Engineering Co Production d'oléfines
US3206522A (en) * 1959-08-10 1965-09-14 Continental Oil Co Production of alpha-olefins
US3352940A (en) * 1963-02-11 1967-11-14 Exxon Research Engineering Co Process for production of nu-alpha-olefins by the alkyl metal technique
DE1443780A1 (de) * 1962-02-27 1969-03-06 Ethyl Corp Verfahren zur gleichzeitigen Herstellung von kleinen alpha-Olefinen und Aluminiumalkylen aus AEthylen
US3696161A (en) * 1970-09-30 1972-10-03 Ethyl Corp A chemical process of separating hydrocarbyl aluminum from olefins by the use of 2:1 complexes of aluminum alkyls and an alkali metal salt
US4314090A (en) * 1980-08-18 1982-02-02 The Dow Chemical Company Linear alpha olefin production
US4380684A (en) * 1981-06-01 1983-04-19 The Dow Chemical Company Linear alpha olefin production using a tank growth reactor
EP0109989A1 (fr) * 1982-11-25 1984-06-13 The Dow Chemical Company Production d'alpha-oléfines linéaires par utilisation d'un réacteur de croissance

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1118188B (de) * 1959-03-17 1961-11-30 E H Karl Ziegler Dr Kreislaufverfahren zur Herstellung von ª‡-Olefinen durch Umsetzung von halogenhaltigen organischen Aluminiumverbindungen mit Olefinen
US3702345A (en) * 1970-10-06 1972-11-07 Gulf Research Development Co Process for converting ethylene to normal alpha olefins
US4484016A (en) * 1983-07-05 1984-11-20 The Dow Chemical Company Process for making a mixture of ethylene and butene-1

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1173508A (fr) * 1956-04-10 1959-02-26 Exxon Research Engineering Co Production d'oléfines
US3206522A (en) * 1959-08-10 1965-09-14 Continental Oil Co Production of alpha-olefins
DE1443780A1 (de) * 1962-02-27 1969-03-06 Ethyl Corp Verfahren zur gleichzeitigen Herstellung von kleinen alpha-Olefinen und Aluminiumalkylen aus AEthylen
US3352940A (en) * 1963-02-11 1967-11-14 Exxon Research Engineering Co Process for production of nu-alpha-olefins by the alkyl metal technique
US3696161A (en) * 1970-09-30 1972-10-03 Ethyl Corp A chemical process of separating hydrocarbyl aluminum from olefins by the use of 2:1 complexes of aluminum alkyls and an alkali metal salt
US4314090A (en) * 1980-08-18 1982-02-02 The Dow Chemical Company Linear alpha olefin production
US4380684A (en) * 1981-06-01 1983-04-19 The Dow Chemical Company Linear alpha olefin production using a tank growth reactor
EP0109989A1 (fr) * 1982-11-25 1984-06-13 The Dow Chemical Company Production d'alpha-oléfines linéaires par utilisation d'un réacteur de croissance

Also Published As

Publication number Publication date
CA2018327A1 (fr) 1990-12-29
DE69023050D1 (de) 1995-11-23
DE69023050T2 (de) 1996-03-21
JPH0348630A (ja) 1991-03-01
US4935569A (en) 1990-06-19
JP2744118B2 (ja) 1998-04-28
EP0405222B1 (fr) 1995-10-18
CA2018327C (fr) 2001-07-24
EP0405222A3 (en) 1992-02-26

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